A new approach to carbon-carbon bond formation: Development of aerobic Pd-catalyzed reductive coupling reactions of organometallic reagents and styrenes.

Alkenes are attractive starting materials for organic synthesis and the development of new selective functionalization reactions are desired. Previously, our laboratory discovered a unique Pd-catalyzed hydroalkoxylation reaction of styrenes containing a phenol. Based upon deuterium labeling experiments, a mechanism involving an aerobic alcohol oxidation coupled to alkene functionalization was proposed.

Direct measurement of the rate of interconversion of zirconaaziridine enantiomers.

The insertion of enantiopure C2-symmetric diphenylethylene carbonate into the Zr-C bonds of zirconaaziridines leads to the asymmetric synthesis of amino acid methyl esters. Because the zirconaaziridine enantiomers interconvert, the reaction is a dynamic kinetic resolution (DKR). The efficiency of the DKR (the ratio of the two diastereomeric products) is determined by the balance between the rate of enantiomer interconversion and the rate of insertion; slow addition of the inserting enantiopure carbonate is often required to maximize the stereoselectivity.